Nicotinium alkyl sulfates



Patented May 16, 1950 ED S5 PATZEN T OF F [GE NICOTINIUM 'ALKYL .SULFATEfi NotDrawinge Application August 11, 1948,

Serial No. 43,778"

3;Clai;ms-, (Cl. 2.60:-291) 1 This invention generally is a continuation-inpart of patent application Serial. NQ ..737,46., led November 9 7* now andQ ed,anal-ent e N,N-dialky1 morpholinium alkyl sulfates, and of patent application SerialNo. 41,728, filed July 30, 1948, entitled,- Unsymmetrical quaternary ammonium. alkyl sulfatesg More specifically the .pr esent invention relates to nicotinium alkylsulfates of the; general formula:

in which R is analkyl radical from one to eighteen carbon atoms, Y. analk-yl or cyclc-alkyl radical from three to eighteen carbon .atoms and. In, either one or two. Nicotinium alkyl sulfatcsoi the above formula. in. which; howeyer B, .and.. Y are identical and alkyl radicals of only one ortwo. carbon atoms (nicotinium methoor etho sulfates) have beenknow lbeforei They are prepared by the actionofequimolar or double molar quantities of di-meth-yl or dieth-y1 sulfate upon nicotine.

The method of preparation involved inthis invention involves the-reaction of nicotine (dor'l, or-dl-) with equimolar, or double molar quantities of a symmetrical or an unsymmetrical di-alkyl sulfate, giving rise to four distinct possibilities as illustrated below:

(b) the; following symmetrical; di-alkyl sulfates have been used: di-n-propyl nebutyl n ai nyln-hexyl-, n-heptyl n-octyl n-decyl lauryl-, myristyl-, cetyland'octadecyl sulfates. Also unsaturated al y u iata s; l. s yeloz liiv sulfates can be employed in the above reactions In carrying out processes (0) and ((1) usually methyl-alkyl sulfates were employed, in which the alkyl radicals were: n-heXyl-, cyclohexyl-, n-octyl-, n-decyl-, (4-t-amyl) cyclohexyl-, lau- 2; ryl-j, myristyl-,.c$tyl and octadecyl. Instead of. the methyls ltates5 cited above, also the corre-m sponding ethylsulfatesmay be used,which, howevennecessitates a longer reaction period.

With.- the many reaction possibilities as outlinedabove, it-is now-possibleto prepare-nicotinium compounds with predetermined properties, such properties manifesting themselves incertain outstanding physical, chemical and: physiological characteristics. These character.- istics involveunusual solubility behaviour-, capillary activity and detergency. Furthermore also intramolecularsynchronization of bactericidal and fungicidal action-:withinsecticidal qualities has beenrealized, Generally, the postulations given in the aforementioned concomitant patent pplications pply. it Qut. ser o also. to this particulan case, which, is, however, much more important as it involves. compounds possessing not only one but two anionoidic, as well as cationoidiccenters, in-.- addition to. thea priori inherent physiological behaviour of. the alkaloid; usedr'in this invention.

Thus :many of-rthe...com-pounds described herein ar detergents and emulsifying agents in both, aqueousand nonraqueousimedia. Many are also, effective, germicides,.- fungicides, and. insecticid es..;

Ejggample le -Nicotinqwzfth symmetrical diealky l 1 4 3 ne-t n h. m l. .of..-re.disti .d; mmer ia 1 tine and-x. one-tenth. mol of; di-n-dQQyL- sulfate (13'; P-145 150?'/81. mm-) are; placed into; a 1 00' cc. round: bqttomedfiyiex-flgsk and th reactants well mixed;.. The;flask;is.w 1-1 s opp red a d mmersecl'into,zanoilg bath he hfi l mixture thenheated" for. twelve. hours at ll 0-1l5?- C After thistirna the.:.rea ction .miXture .is allowed to cool. Fifty cc. of ether is then added to the cold reaction mixture-- and the mass Well stirred. Finally, after attaching-a water reflux condenserto the. flask,- the..- mixture is. gently.- heated in waterbath-- at about 35-5109 0. for. about lam-inutes. During this heating period thecontent of 1 the-flask is either well stirred or shaken repeatedlye Then the reactionmigzture is allowed to cool-and the ether layer decanted off: The procedure... of. ether extraction. is. repeated. twice to. eve cmple elv any. ematite. star n m w terials Th ether insoluble residue isrccrystallized; frprn v hotethyl; alcohol The N iflyle. ium neulfate husr duc s a sits t; 78479,? G. is.inso.luble,in"ether; but: so uble inhotalcohol, acetone. or. ethyl acetate. Itforrhs.v foaming solutions with water.

Using the above procedure the following N- alkyl nicotinium alkyl sulfates were prepared using redistilled commercial nicotine and equimolar quantities of the symmetrical di-alkyl sulfates indicated below:

Compounds: Mono sulfates Di-alkyl Sulfates (1 mol) N n-Propyl-Nicotinium n-propyl Di-n-propyl. N-n-Butyl-Nicotiniiun n-butyL. Di-n-butyl. N-n-Amyl-Nicotinium u-amyL Di-n-amyl. N-n-Hexyl-Nicotiuium n-hcxyL. Di-n-hcxyl. N-n-Octyl-Nicotinium n-octyl Di-n-oct N-Lauryl-Nicotinium lauryl (M. P. 8284 0.) Di-lauryl N-Myristyl-Nicotinium myristyl (M. P. 7477 Di-my-ristyl N-Oetyl-Nicotinium cetyl (M. P. 7273 0.) Di-cetyl. N))ctadecyl-Nicotinium octadecyl (M. P. 7680 Di-octadccyl.

Employing the same experimental procedure, but using double molar quantities of the symmetrical di-alkyl sulfate and redistilled commercial nicotine, the following N,Ndi-alkyl-nicotinium di-alkyl sulfates were prepared:

Example 2.-Nicotz'ne with unsymmetrical di-alkyl sulfates One tenth mol of redistilled commercial nicotine and one fifth mol of methyl-cetyl sulfate (M. P. 7273 C.) are introduced into a 100 cc. round bottom Pyrex flask, the two reactants are well mixed, and the flask well stoppered. The flask is then heated on a steam bath, at a temperature of about 90 C. for about forty hours. After this time the contents of the flask are allowed to cool. Afterwards the solid reaction mixture is broken up and is then triturated with 50 cc. of ether, first in the cold and later with warming on a steam bath. After cooling, the ether layer is decanted off. This procedure is repeated twice. The final product is crystallized from boiling ethyl alcohol. 'The compound, the N,N-dimethyl-nicotinium di-cetyl di sulfate melts at 163-165 C. (uncorn). It is insoluble in ether, but soluble in hot ethyl acetate, ethyl alcohol and acetone.

Following the procedure given above, the using equimolar quantities of nicotine and the unsymmetrical methyl-alkyl sulfates enumerated below, the following N-methyl-nieotinium alkyl sulfates were obtained:

Methyl-alkyl sulfates (1 Compounds: Mono sulfates mol) -cetyl. -octadecyl.

Mothyl-alkyl Compounds: Dr-Sulfates sulfates (2 mols) N,N-Dimethyl-Nicotinium di-n-hexyl -11-hexyl. N,N-Dimethyl-Nicotiuium di-n-octyl -n-octyl. N,N-D mcthyl-Nicotinium di-n-decyl -n-decyl. NgliDlmethyl-Niootinium di-lauryl (M. I. 157-100" -leuryl. N,I i-l)methyl-Nicotinium di-myristyl (M. P. 158- -myristyl.

1 N,1%Pci}n;cthy1-Nicotiuium di-octadccyl (MP. -octadccyl.

Compounds: Equionics Di-alkyl sulfates N ,li-Dimethyl-Nicotinium di-n-hexyl di sule. N,N-Dimethyl-Nicotinium di-cyclohcxyl disulfate. N-Methyl-Nicotinium (4-t'amyl) cyclohoxyl sulfate.

methyl-n-liexyl (2 mols) methyl -cyclohexyl (2 mols).

methyl-(4-tamyl) cyclohcxyl (1 mol).

What we claim is: 1. Nicotinium alkyl sulfates of the general formula:

in which R is an alkyl radical from one to eighteen and Y an alkyl radical from six to eighteen carbon atoms and a: one and two.

2. Nicotinium alkyl sulfates of the general formula:

in which R is an alkyl radical from on to eighteen and Y an alkyl radical from six to eighteen carbon atoms.

3. Nicotinium alkyl sulfates of the general formula:

in which R is an alkyl radical from one to eighteen and Y an alkyl radical from six to eighteen carbon atoms.

JOSEPH B. NIEDERL. MARTIN E. MCGREAL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,915,334 Salzbcrg et al June 27, 1933 2,042,023 Schonhofer May 26, 1936 2,104,728 Bertsch et al Jan. 11, 1938 2,115,250 Bruson Apr. 26, 1938 2,152,047 Hohl et a1 Mar. 28, 1939 2,232,662 Hockenyos Feb. 18, 1941 2,247,266 Wibaut June 24, 1941 2,256,877 Bertsch Sept. 23, 1941 2,271,707 Munz Feb. 3, 1942 2,380,325 Niederl et a1 July 10, 1945 2,456,851 Woodward et a1 Dec. 21, 1948 FOREIGN PATENTS Number Country Date 743,973 France Apr. 10, 1933 OTHER REFERENCES Beilstein: Organische Chem, vol. XXIII (1936), p. 114. 

1. NICOTINIUM ALKYL SULFATES OF THE GENERAL FORMULA: 